Enamel lacquer or varnish.



UNITED STATES PATENT oFFIcE.

Jonas w. AYLSWORTH, or nnsr centres-new JERSEY, ASSIGNOR, BY nrencr m MESNE ASSIGNMENTS, TO oounnnsrrn company or AMERICA, or EAST cannon, .NEWJERSEY, A ooRronA'rIoN on NEW JERSEY.

ENAMEL LACQUEB OR VARNISH.

No Drawing.

Specification 01 Letters Patent. Application filed February 11, 1910. Scria1 No. 543,239.

Patented June 2, 1914.

new and useful Enamel Lacquer or Varnish,

of which the following is a description.

My invention relates to a new composition of matter which is adapted especially for use as an enamel lacquer or varnish or as an ingredient of the same, and my object is the production of such a composition and an improved process for the formation of the same.

While my improved composition is adapted especially for use in the production of a varnish or enamelwhich hardens on subsequent heat treatment, it also, in its broad aspects, forms the basis for an improved composition suitable for forming a cement for pipe joints and the like, which I have described and claimed in Patent No. 1,065,- 195, granted June 24, 1913. In this application, I will claim my improved composition in terms sufficiently broad to cover the same in its broadest aspects as applied either to a cement or a varnisln'and will also append,

claims to the composition as adapted particularly to the manufacture of the varnish or enamel and process for making the same.

My invention contemplates such an enamel as is adapted to be formed on metals and .wood, to form a hard surface on cardboard,

' fabric, paper, leather, etc., to form a surface adapted for embossing operations, making negative matrices for engraving and printing, forming a hard surface suitable for molding sound records, and incorporating with various inert pulverized materlals and pigments to form veneers for wood. It also is adapted to be incorporated with woven fabrics or paper to form bindings for books, and in the manufacture of a variety of articles. L q

My invention comprises broadly a fusible resin of phenolic origin, wluch has mlxed therewith a substance which is adapted to react with the resin upon the application of suflicicntheat to form a hard insolubleeondensation product.

More specifically, my invention comprises a varnish resin which is soluble 1n the usual solvents of shellac, and which may range from pale amber to various shades of transparent brown in color, and which hardens onthe application of heat at a temperature of from 170 to 220 degrees F., or higher.

the varnish upon heating, as described,

forms a refractory enamel more refractory than ebonite or hard rubber, and almost equaling ivopy inhardness and strength. It is at the same time more capable than are the substances mentioned of Withstanding the action of chemical agents and heat.

My improved varnish composition is.

formed by the incorporation of substances containing the methylene radical CH preferably heXa-methylene-amin or hexa-methylone-tetra-amin', as it is sometimes called (0H,),N, with a phenol resin, such as is described in my application Serial No.

496,060, plastic composition and process of manufacturlng the same, filed May 14, 1909,

and Patent No. 1,029,737, granted June 18,

1912. Or, in place of hexa-methylene-tetraamin, I may use the product obtained by reacting upon aqueous solutions of ammonia with formaldehyde or polymers thereof, which product may contain other methyleneamins, as explained in my Patent No. 1,020; 593, granted March 19, 1912. Various of the so-called shellac substitutes of phenolic or cresolic origin may however be substituted for the phenol resin referred to above, with good results, in many of the uses of enamel. The resin or shellac substitute and the methylene-amin are dissolved in a suitable solvent such as alcohol, acetone or equivalent solvent. The methyleneamin compound performs the function of reacting with the fusible phenol condensation product or phenol resin 11 on the application of suificient heat to harden the same by transforming it into an infusible final condensation product, as is .described in my Patent No. 1,020,593, referred to. This result is apparently accomplished by the union of the methylene radical contained in the methylene-amin with .the phenol resin, the nitrogen component of the hardening mgredient uniting with hydrogen from the phenol resin to form ammonia, which remains in unstable-"combination w1th1n the mass, or v which may be evolved by heat. llhis ammonia is evolved, with comparative ease. The hexa-methylene-amin or other methylene-amin compound seems to be the most suitable hardening substance which can be used, although other substances containing the methylene radical, as formaldehyde, trioxymethylene, etc., may be used. With the methylene-amin compounds, however, there is never any danger of losing any of the same.

by evolution as gas, if the composition is to remain for'some time before its application and hardening by heat treatment, since the methylene-amin only gives up its methylene by combination with such a substance as the phenol resin upon heat treatment.

I prefer, as I have stated, to use the particular phenol resin described inmy application Ser. No. 496,060, referred to, and Patent No. 1,029,737 rather than any of the shellac substitutes mentioned, for mixture with the hardening agent, and for many purposes the mixture with this described resin has particular advantages. My phenol resin, as described in the said application, is a fusible, soluble, phenol-formaldehyde condensation product, in which the formaldehyde is all combined with the phenol, and there is no free phenol, or only a small, ascertainable amount. This resin is a final product, in the sense that it cannot be transformed into the infusible insoluble product by any amount of heating, at any temperature, either alone or with basic or acid condensing agents. It

is preferably completely dehydrated by heating to about 400" F. It is" preferably formed without the use of any condensing agent. When hexa-methylene-tetra-amin or a solid anhydrous polymerized formaldehyde like tri-oxymethylene is used as the hardening agent, it should be noted that this ingredient also is anhydrous.

The ingredients may be separately dissolved in the solvent and mixed, or they may be dissolved together. Or, the mythyleneamin and the phenol resin may be mixed while the resin is in fused condition at from 200 to 230 degrees F. without the use of a solvent. This mixture may then be rolled when it has cooled sufliciently to become asty into'thin sheets or laminae suitable for eing dissolved in the solvent, or the material may be formed in thin sheets by other means. The last described form of the composition is desirable for many uses, as it may be sold and transported in dry state in rolls, the purchaser or user dissolving the same in a suitable solution when he is ready to apply .the composition. in the same manner as shellac is transported and used. The composition formed with a methylene-amin compound may be kept indefinitely in solution in closed receptacles without harmful change. It is non-corrosive -to metals either in solution or dry, and forms an eflicient preservative coating for metals to prevent oxidation and other corrosive actions.

When the methylene-amin compound is mixed with the phenol resin in the fused state, the and rolling of the material are carried out without change of the material into the hard infusible product, since the hardening reaction does not take place immediately, but is gradual at the temperature required for the mixing of the ingredients. Hardening of the film of varnish or enamel after evaporation of the solvent takes place at quite moderate temperatures and is greatly accelerated by increased temperatures. This hardening requires no compensating pressure to prevent frothing or the formation of bubbles, and the film is formed without cracks or other defects due to the evolution of gas during the final reaction of the ingredients. The varnish or enamelmayl be hardened by passing gives out radian heat over the surface of the enamel film c ose to the same, but not in contact therewith. Thus, a heated flat iron, electric heater, or similar heating device, may be used.

Suitable proportions of the liquid enamel or varnish are 100 parts of phenol resin, 8 to 10 parts of hexa-methylene-amin, 100 to 500 parts of solvent which may be wood alcohol, methylated spirits, grain alcohol, denatured alcohol, acetone, or mixtures of the same with each other or with small percentages of water.

When the liquid enamel or lacquer is designed to be used as a protective coating on metal, the proportion of the hexa-methyleneamin may be reduced to from 4: to 6 parts to 100 parts of the phenol resin. When the liquid enamel or lacquer is designed to be used a film applied to a suitable backing to be embossed or shaped after evaporation of the solvent and hardening by heat, a solid solvent ingredient such as those mentioned in application Serial No. 496,060, or Patent No. 1,020,593, above referred to, may be added in percentages which may be varied between 5 and 25 per cent., dependent upon the particular use desired, the nature of the solid solvent and its solubility in the volatile solvent used in the lacquer. The solid solvents any body who mentioned in application Ser. No. 496,060,

a'sthere described are termed final product solvents by which term are included only such substances as will dissolve the ultimate condensation product or combine therewith at the baking temperature, render it plastic at such temperature, and remain as a part of the product in the condition of solid'solution, both when the ultimate product is hot and when it is cold. Among the examples of this class which may be mentioned are naphthalene and some of its derivatives, such-as nitro and chloro derivatives, especially the mono-nitro and di-nitro and monochloro and tetra-chloro naphthalenes,-di nitro benzene, preferably the meta variety, acetanilid, ricinoleic acld and ricinelaidic acid and their anh drids, benzoic acid and anhydrid, and di-p enylamin.

As stated, my invention comprises the maingredient for the same and the process for making the same, and italso comprises the substance broadly as a new composition of matter comprising a fusible phenol resin having mixed therein a small percentage of a substance which combines with the resin on application of sufiicientheat to harden it, together with a suitable solvent if desired. As I have stated, this composition also forms the basis of an improved cement which I describe and claim inPatent No. 1,065,495, abovereferred to.

Havingnow described my invention, what I claim and desire to protect by Letters Patent is as follows:

1. A new composition of matter comprising a mixture of a fusible soluble phenol resin which is anhydrous and contains substantially no free formaldehyde or equivalent and a substance which is soluble in common solvents and is capable of combining with the said resin on application of heat to harden the same to-infusibility and insolubility, the said resin being character ized by its incapability of transformation into an infusible and insoluble 'body, when not mixed With such a substance, substantially as described.

2. A new composition of matter compris-.

ing amixture of a fusible soluble phenolformaldehyde condensation product containmg substantially no free formaldehyde, and hexa-methylene-tetra-amin, capable of combinmg with said product on application of heat, and suiiicient in quantity to harden said product to infusibility and insolubility, by combination therewith, substantially as described.

3. Anew composition of matter comprising a mixture of a fusible soluble phenol resin, a normally non-volatile solid solvent ingredient, and a substance which is soluble in common solvents and is capable of combining with the said resin on application of heat to harden the same to infusibility and insolubility, the said resin being character- 1zed by its in-capability of transformation lnto an infusible and insoluble body, when not mixed with such a substance, substantially as described.

. A. A new composition of matter comprislng a m1xture of a fusible soluble, anhydrous phenol resm, and an anhydrous methylenecontaining substance, substantially as described.

5. A new composition of matter comprismg a mixture of a fusible, soluble phenol resin, hexa-methylene-tetra-amin, and asolid solvent ingredient, substantially as described. 6.- A new composition of matter comprismg a mixture of a fusible, soluble anhydrous non condensing agent containing phenol resln, and a substance which is soluble in common solvents and is capable of combining with the said resin 011 application of heat to harden the same to infusibility and insolu bility, substantially as described.

I. As a new article of manufacture, an ingredient adapted to be dissolved in a suitable solvent to form a hard varnish or lacquer on subsequent heating, comprising a fusible phenol. resin having mixed therein a small percentage of hexa-methylene-tetraamin and formed in thin sheets, substantially as described. 7

8. As a new article of manufacture, an ingredient adapted to be dissolved in a suitable solvent to form a hard varnish or lacquer on subsequent heating, comprising a fusible phenol resin having mixed thereina small percentage of hexa-met-hylene-tetraamin and a solid solvent ingredient, and formed in thin sheets, substantially as dedescribed.

9.. The process of preparing an ingredient for a varnish or enamel composition which consists in preparing without the use of a condensing agent a fusible soluble phenol resin which is incapable of transformation into an infusible and insoluble b'ody, when not mixed with an added hardening agent, and which resin is anhydrous and contains substantially no free formaldehyde or equivalent, and mixing the same thoroughly with a substance which is soluble in common solvent and is capable of combining with said resin on application of sufficient heat to harden the same to infusibility and insolubility, the mixture being made under such conditions as not to cause the said hardening reaction, substantially as described.

10. The process of preparing an ingredient for a varnish or enamel composition which consists in preparing a fusible soluble anhydrous phenol resin, and mixing the same thoroughly with an anhydrous methylenecontaining hardening agent therefor, under such conditions as not to cause the said agent to react with the said resin during the mixture, substantially as described.

11. The process of preparing an ingredient for a varnish or enamel composition which consists in preparing a fusible soluble phenol resin which is incapable of transformation into an infusible'and insoluble body, when not mixed with an added hard ening agent, and mixing the same thoroughly with a small amount of hexa-methyL enetetra-amin, under such conditions as not to cause reaction in the mixture between the said substances, substantially as described.

12. The process of preparing an ingredient for varnish adapted to be dissolved in a suitable solvent and subsequently hardened by heating, which consists in mixing a small percentage of hexa-methylene-tetrziamin with a phenol resin in fused condition,

permitting the substance to become pasty,-

and rolling in thin sheets, substantially as described.

13. The process of preparing an ingredient for varnish adapted to be dissolved in a suitable solvent and subsequently hardened by heating, which consists in mixing with a phenol resin in fused condition a small percentage of a substance which reacts with the same on application of sufficient heat to form a hard product, and' withdrawing the heat before the substance has hardened, substantially as described.

14. The process of preparing an ingredi ent for varnish adapted to be dissolved in a suitable solvent and subsequently hardened by heating, which consists in mixing witha phenol resin in fused condition asmall percentage of a substancewhich. reacts with the same on application of suf- 

